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CN102015803B - 阳离子成膜聚氨酯的水性分散体 - Google Patents

阳离子成膜聚氨酯的水性分散体 Download PDF

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CN102015803B
CN102015803B CN2009801148802A CN200980114880A CN102015803B CN 102015803 B CN102015803 B CN 102015803B CN 2009801148802 A CN2009801148802 A CN 2009801148802A CN 200980114880 A CN200980114880 A CN 200980114880A CN 102015803 B CN102015803 B CN 102015803B
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V·阿兰佐
G·科斯塔
D·孔蒂
G·利巴希
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Abstract

本发明揭示一种稳定的成膜阳离子聚氨酯的水性分散体，该分散体是通过用水或胺对一种阳离子预聚物进行增链反应制备的，该阳离子预聚物由脂族二异氰酸酯、具有两个能与-NCO基团反应的羟基的脂族叔胺、线型多元醇和甲磺酸得到的。

Description

阳离子成膜聚氨酯的水性分散体
发明领域
本发明涉及成膜阳离子聚氨酯的水性分散体，以及它们在制备化妆品和个人护理产品中的应用。
依据本发明的一个基本方面，描述了制备上述水性分散体的步骤。
背景技术
能生产膜的阳离子聚氨酯(成膜聚氨酯)的水性分散体是已知的；在多个专利中描述了它们的制备以及它们在许多工业领域如化妆品、织物、皮革和纸业领域中的应用。
例如，US 3,388,087描述了季铵化聚氨酯水性分散体的制备，该分散体可用于制备能用在化妆品工业中作为固定发蜡组分的挠性膜。
US 3,480,592描述了含盐化的叔胺基的聚氨酯的水性分散体的制备；由这些聚氨酯得到的膜具有与US 3,388,087类似的用途。
最近，US 6,335,003报导了含盐化的叔胺基的聚氨酯的制备；US6,335,003所述的聚氨酯具有高胺值，与US 3,480,592所述的聚氨酯不同。
US 2004/0052753描述了含盐化的叔胺基的弹性聚氨酯以及它们在化妆品组合物中的应用。
至少假设，阳离子成膜聚氨酯水性分散体可成为常规使用的脲-甲醛树脂的有效代替品，使用该阳离子成膜聚氨酯水性分散体变得越来越重要，这是因为对个人使用的产品(包括织物)中甲醛残留物的管理要求越来越严格。
但是，市场上这类产品的供应非常少。
在制备成膜阳离子聚氨酯水性分散体中遇到的主要问题是它们组分之间的平衡，必需同时确保在水中良好的分散性和稳定性，以及良好的弹性。
目前申请人已经发现通过在制备过程中使用脂族二异氰酸酯和甲磺酸作为聚合物叔胺基的盐化剂可以得到非常稳定的成膜阳离子聚氨酯的水性分散体。
水性分散体稳定性提高除了对其储存能力有正面影响外，还能有利地提高由该水性分散体得到的膜的透明度和光泽。
就本申请人所知，脂族二异氰酸酯与甲磺酸的组合的稳定化效应至今为止是未知的，即使US 3,480,592中提及了甲磺酸(第4栏第32行到第5栏第60行)，也只是将其作为罗列的可用作阳离子聚氨酯盐化剂的化合物中的一种。
说明
因此，本发明的一个基本目的是通过以下步骤得到的成膜阳离子聚氨酯的水性分散体：A)使一种或多种脂族二异氰酸酯与具有两个能与-NCO基团反应的羟基的脂族叔胺和分子量为500-5,000的多元醇聚醚或多元醇聚酯型线型多元醇反应，得到具有游离异氰酸酯基的预聚物；B)用甲磺酸使预聚物的胺基盐化；C)用水或胺对这样得到的阳离子预聚物进行增链。
在步骤A)中，脂族二异氰酸酯与具有两个活性羟基的化合物(线型多元醇和脂族叔胺)的摩尔比为1.2-2.2，优选为1.3-1.8。
本发明的阳离子聚氨酯的分子量为2,000-50,000。
可依据本发明使用的二异氰酸酯是脂族二异氰酸酯；术语“脂族”包括脂族和脂环族；优选的二异氰酸酯选自：4，4’-二环己基甲烷-二异氰酸酯，1-异氰酸酯，3-异氰酸酯-甲基-3，5，5-三甲基环己烷(或异佛尔酮二异氰酸酯)，1，6-己二异氰酸酯和它们的混合物。
具有两个能与-NCO基团反应的羟基的脂族胺优选是3-(二乙基氨基)-1，2-丙二醇或烷基二乙醇胺；在烷基二乙醇胺中，特别优选的是甲基二乙醇胺、乙基二乙醇胺、异丙基二乙醇胺、正丁基二乙醇胺、叔丁基二乙醇胺、环己基二乙醇胺、正己基二乙醇胺和它们的混合物。
聚氨酯中结合的胺的量用胺的毫当量数表示，通过胺的毫摩尔数与干聚氨酯克数的比值的百分数来计算。
在本发明中，聚氨酯中胺的毫当量数为20-150，优选为30-90。
可用于本发明的线型多元醇的分子量为500-5,000，优选为800-3,000，它们优选是羟基封端的聚醚或聚酯二醇。
可依据本发明使用的多元醇聚酯的例子是由具有4-9个碳原子的酸或酸酐(优选是脂族类的)与具有2-8个碳原子的脂族二醇经过缩聚得到的产物。
在优选的多元醇聚酯中，我们列举由1，4-丁二醇和乙二醇得到的聚己二酸酯，由1，6-己二醇和新戊二醇得到的聚己二酸酯，由1，6-己二醇得到的聚己二酸酯邻苯二甲酸酯，聚己内酯和由1，6-己二醇和1，4-丁二醇得到的聚碳酸酯二醇。
特别优选的是由1，4-丁二醇和乙二醇得到的聚己二酸酯，由1，6-己二醇和新戊二醇得到的聚己二酸酯，由1，6-己二醇得到的聚己二酸酯邻苯二甲酸酯。
可使用的多元醇聚醚的例子是聚乙二醇、聚四氢呋喃和它们的混合物；后者优选用于实现本发明。
在步骤A)中可使用不同线型多元醇的混合物。
在大多数普通实施方式中，步骤A)在无任何溶剂的情况下进行，但是优选在步骤A)结束时但在进行步骤B)的盐化处理之前，加入非反应性有机溶剂，例如N-甲基吡咯烷酮或丙酮。
盐化优选在室温下使用甲磺酸进行，甲磺酸的形式为其常规可购得的形式之一，即70％w/w的水溶液。
通过加入摩尔量为60-120％、更优选95-105％的甲磺酸来进行盐化步骤，该摩尔量百分数是基于叔胺的摩尔数。
步骤B)中得到的阳离子聚氨酯的增链反应优选通过在20-60℃的温度下与水反应来进行。
通常，在最终的水性分散体中，成膜阳离子聚氨酯的含量为20-35重量％。
该浓度范围特别适用于工业应用，因为这相当于充分浓缩的分散体，避免了不必要的大量水的运输；同时，该浓度范围内的分散体的粘度使其很容易被操作。
而且，依据本发明所述，还可以得到不含溶剂且只含有少量挥发性有机化合物的阳离子分散体。
本发明的成膜聚氨酯水性分散体可有利地用于制备化妆产品，例如上妆产品(睫毛膏，长效唇膏)、发蜡(hair lacquers)、指甲油、发用啫喱(hairgels)、防水型防晒霜。
本申请分散体的阳离子性质使它们对角蛋白、进而对头发有特别强的亲合性；它们能有利地用在头发处理和护理产品中。
除了化妆品领域外，本发明的分散体可用于皮革修饰，织物上胶和修饰，纸、木材和塑料的涂敷中，还可用作羊毛的抗毡合剂。
在以下实施例中，描述了依据本发明的水性分散体的制备(实施例I-III，V)和对比分散体的制备(实施例IV，VI-VIII)；所描述的百分数是重量百分数。
在应用实施例中，描述了由依据本发明的水性分散体制备发蜡。
实施例
在实施例中使用以下材料：
多元醇1＝由1，4-丁二醇和乙二醇得到的聚己二酸酯，分子量为830克/摩尔；
多元醇2＝聚四亚甲基醚二醇，分子量为1,000克/摩尔；
胺1＝甲基二乙醇胺(分子量为119.16克/摩尔)；
胺2＝3-(二乙基氨基)-1，2-丙二醇(分子量为147.22克/摩尔)；
酸1＝甲磺酸(分子量为96.11克/摩尔)，70％的水溶液；
酸2＝对甲苯磺酸(分子量为172.2克/摩尔)，20％的水溶液；
酸3＝磷酸(分子量为98.00克/摩尔)，75％的水溶液；
酸4＝甲酸(分子量为46.03克/摩尔)，85％的水溶液；
二异氰酸酯1＝4-4’-亚甲基-二-(4-环己基异氰酸酯)，分子量为262.35克/摩尔(Desmodur W，拜尔(Bayer))；
二异氰酸酯2＝1，6-己二异氰酸酯，分子量为168.19(Desmodur I，拜尔)；
二异氰酸酯3＝甲苯二异氰酸酯，分子量为174.16(Desmodur T80，拜尔)。
实施例I
依据本发明的阳离子聚氨酯分散体的制备。
在氮气气氛和室温下，向配有内部温度计、搅拌器和冷却器的反应容器中加入160.21克(160毫摩尔)多元醇2(在40℃进料)，17.87克(150毫摩尔)胺1和0.048克苯甲酰氯。将该混合物加热到40℃，搅拌30分钟。在搅拌下将121.91克(465毫摩尔)二异氰酸酯1加入到该均匀混合物中，然后在60℃保持30分钟。将反应温度升高到90℃，直到滴定确定仍然存在的游离-NCO基团的计算值为4.35重量％(在该实施例和其它实施例中该值都是依据标准方法ASTM D2572确定的)。
在得到上述NCO值后，立即将预聚物冷却到60℃，同时加入105克丙酮。在约40℃，在搅拌下加入20.59克(150毫摩尔)酸1，10分钟后，在40℃加入679.3克软化水。
然后，在真空下蒸馏除去丙酮，同时保持对阳离子水性聚氨酯分散体的搅拌，得到固体含量为30％的稳定的半透明产品。
在蒸馏过程结束时，红外光谱中2240厘米-1处的-NCO峰消失。
得到的阳离子水性聚氨酯分散体可以稳定6个月以上。
实施例II-VIII
进行实施例I的步骤，但是如表1a(依据本发明的实施例)和表2a(对比例)所示改变比例和原料。
表1b和2b报导了聚氨酯分散体的特性。
表1a(原料量)
Figure BPA00001250270700051
 胺2   -   -   -   22,08   150   -   -
 二异氰酸酯1   121.91   465   44.45   169   40.77   155   40.25   153
 二异氰酸酯2   -   69.33   412   63.58   378   62.77   373
 酸1   20.59   150   20.59   150   20.59   150   22.65   165
 软化水   679.25   679.25   679.0   670
 丙酮   105   110   110   110
表1b-分散体性质
 实施例I   实施例II  实施例III  实施例V
 ％NCO预聚物  4.35％   4.94％  4.53％  3.84％
 固体含量  30％   30％  30％  30％
 储存期限  ＞6个月   ＞6个月  ＞6个月  ＞6个月
表2a(原料量)
*对比例
表2b-分散体性质
 实施例IV*  实施例VI*   实施例VII*  实施例VIII*
 ％NCO预聚物   4.35％   3.3％   4.5％   4.8％
 固体含量   N.D.   33％   30％   N.D.
 储存期限   30’   60’   80’   0**
*对比例
**在制备过程中分散体分离。
应用测试
制备两种标准制剂来评价由实施例I得到的产品与用在头发造型化妆品中的标准成膜聚合物的性能比较。所使用的对比聚合物是聚乙烯基吡咯烷酮/乙酸乙烯酯(CTFA名称：VP/VA共聚物，LUVISKOL
Figure BPA00001250270700071
VA64 P，来自巴斯夫公司(BASF Aktiengesellschaft))。
所述制剂具有以下组成(a.c.＝活性含量)：
制剂1：
由实施例1得到的分散体(a.c.30％w/w)      6％
水/乙醇混合物1/2                        至100％
制剂2：
LUVISKOL VA64P(a.c.＞95％w/w)           1.8％
水/乙醇混合物1/2                        至100％
将两种成膜聚合物即由实施例I得到的聚氨酯和Luviskol VA64 P完全溶解在水/乙醇混合物中，将制剂1和2转移到喷雾容器中。
为了测试它们的成膜效果，将各1克两种试剂分别喷洒到一缕头发上，干燥1小时。对10人进行的评审测试显示由制剂1得到的修饰效果较柔和。
为了测试卷曲保持性，将各1克两种试剂喷洒到中等/较长长度的一缕头发上，用卷发夹固定1小时。对10人进行的评审测试显示由制剂1得到的修饰效果更自然，卷发更有型。
因此，需要指出由实施例I得到的聚氨酯分散体对头发表现出良好的修饰性能和固定效果。

Claims (12)

1.一种成膜阳离子聚氨酯的水性分散体，该分散体通过以下步骤制得：A)使一种或多种脂族二异氰酸酯与具有两个能与-NCO基团反应的羟基的脂族叔胺和分子量为500-5,000的多元醇聚醚或多元醇聚酯型线型多元醇反应，得到具有游离异氰酸酯基的预聚物；B)用甲磺酸使预聚物的胺基盐化；C)用水对这样得到的阳离子预聚物进行增链；其中，所述线型多元醇是羟基封端的聚醚或聚酯二醇。
2.如权利要求1所述的成膜阳离子聚氨酯的水性分散体，其特征在于，在步骤A)中，脂族二异氰酸酯与线型多元醇和脂族叔胺之和的摩尔比为1.2-2.2。
3.如权利要求2所述的成膜阳离子聚氨酯的水性分散体，其特征在于，二异氰酸酯选自：4，4-二环己基甲烷-二异氰酸酯，异佛尔酮二异氰酸酯，1，6-己二异氰酸酯和它们的混合物。
4.如权利要求3所述的成膜阳离子聚氨酯的水性分散体，其特征在于，具有两个能与-NCO基团反应的羟基的脂族叔胺是3-(二乙基氨基)-1，2-丙二醇或烷基二乙醇胺。
5.如权利要求4所述的成膜阳离子聚氨酯的水性分散体，其特征在于，烷基二乙醇胺选自：甲基二乙醇胺、乙基二乙醇胺、异丙基二乙醇胺、正丁基二乙醇胺、叔丁基二乙醇胺、环己基二乙醇胺、正己基二乙醇胺和它们的混合物。
6.如权利要求4所述的成膜阳离子聚氨酯的水性分散体，其特征在于，所述多元醇是由1，4-丁二醇和乙二醇得到的聚己二酸酯，由1，6-己二醇和新戊二醇得到的聚己二酸酯，或由1，6-己二醇得到的聚己二酸酯邻苯二甲酸酯。
7.如权利要求4所述的成膜阳离子聚氨酯的水性分散体，其特征在于，所述多元醇是聚四氢呋喃。
8.如以上权利要求中任一项所述的成膜阳离子聚氨酯的水性分散体，其特征在于，盐化步骤通过加入摩尔量为60-120％的甲磺酸来进行，该摩尔量百分数是基于叔胺的摩尔数。
9.如权利要求8所述的成膜阳离子聚氨酯的水性分散体，其特征在于，对步骤B)后得到的阳离子聚氨酯的增链反应通过在20-60℃的温度下与水反应来进行。
10.如权利要求1-7中任一项所述的成膜阳离子聚氨酯的水性分散体，其特征在于，成膜阳离子聚氨酯的含量为20-35重量％。
11.包含如权利要求1-10中任一项所述的成膜阳离子聚氨酯的水性分散体的化妆品组合物。
12.如权利要求1-10中任一项所述的成膜阳离子聚氨酯的水性分散体在制备化妆品组合物，皮革修饰，织物上胶和修饰，纸、木材和塑料的涂敷，以及用作羊毛的抗毡合剂中的应用。
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